Photographic silver halide emulsion layers



Patented Nov; 7, 1939 'NITED STATES arr-11w OFFICE I I PHOTOGRAPHIC S IiZTZSSiIlQLIDE EMULSIilN Y Wilhelm Schneider and Max Hagedorn, Dessau, Germany, assignors, by mesne assignments, to Agfa Ansco Corporation, Binghamton, N. Y., a corporation of Delaware 7N0. Drawing. Application July 15; 1936, Serial 7 Claims;

Our present invention relates to the manufac opment (chromogenic development) color pictures can be obtained photographically as described, for instance, in.U. S. Patent No. 1,102,028.

Attempts have been made toproduce multi-color pictures by the process of the said patent 1 raised temperature.

by superimposing a number of suitably sensitized films capable of being developed in the color they are sensitized for. This process must, however, remain without practical application since all the compounds capable of color development recommended in the prior art are soluble in alkali even when incorporated in the layer and'diffuse from the layer of selective sensitivity to which they are allotted into the adjacent layers or into the developing bath.

According to this invention it has been found that several superimposed layers can bedeveloped in color without the fault of difiusion- This ispossible if the components used in the colors are of such character that in spite of good solubility in water they are so firmly held by the gelatin that difiusion froin the layer is not possible. This property is secured by using productsof reaction of certain derivatives of highly polymeric carboxylic acids with bodies adapted by known reactions to form dyestuifs,

for example, amines, phenols, aminophenols, 1 naphthols, aminonaphthols and bodies with the ticularly if the solubility in water is not suilicient. Thus, layers containing these bodies are suitable for formingthe required multi-layer material, since diffusion from one layer to another cannot occur.

The aforesaid phenols and compounds having In Germany July 16, 1935 reactive methylene groups yield a color picture by simple development or may be converted by a 'diazo-process coupled with the photographic process into an azo-dyestufi picture. Substances such as leuco'bodies may be caused to react with the highly polymeric substances which then yield a dyestufi picture by the photographic process. Two or more such layers combined are specially suitable for making pictures in color.

Suitable highly polymeric carboxylic acids and substances like polyglycuronic acids, prote'inaminc acids or synthetic compounds from unsaturated organic acids such as polyvinylcarboxylic acids (polyacrylic acid alone or as a mixed polymerizate with styrene, vinylchlorida'vinylether or nitrogeneous vinyl compounds such as vinylcarbazole or the like), polymerizates of maleic acid, fumaric acid, methylene-malonic acid, alone A or as mixed polymerizates with vinyl compounds. These polycarboxylic acids are caused to react in the form of their acid chlorides or anhydrides or esters or other reactive derivatives with the aforesaid reactive amines, phenols and bodies with active methylene groups, for example with aminophenols, phenylenediamines, aminonaphthols,

aminoacetic acid anhydrides, aminobenzoylaceticacid esters, aminophenylmethylpyrazolones, hydroxynaphthoic acid aminoarylides, diazo-bodies, leuco-dyestuffs, or the like,

The following examples illustrate the invention:

Example 1.--l gram of a condensation product from metaaminophenylmethylpyrazolone and the mixed polymerizate from vinylchloride and maleic acid anhydride' are ground with 5 cc.,.oi caustic soda lye of 5 per centstrength and then dissolved in water. The solution is added to 100 cc. of silver bromide emulsion. A layer of this emulsion may be developed with para-amlnodimethylaniline to a picture which consists of a red dyestufl after the separation of the silver.

Example 2.The procedure is as described in.

Example-1, but instead of a pyrazolone and a condensation productv there is used. one made from 1.-5.-aminonaphthol and the mixed polymerizate namedin Example 1; the layer made yields a picture in a blue dyestufl.

What we claim is:

1. A photographic silver halide gelatin emulsion containing a dyestuficomponent fast to diiiusion with respect to the gelatin, said dyestuff component being anamide of a color former with a highly polymeric carboxylic acid capable of forming a dye at the places of the silver image upon being contacted with a color forming developer. v

2. A photographic silver halide gelatin emulsion containing a dyestuil component fast to diffusion with respect to the gelatin, said dyestufi component being an amide of a color former with a highly polymeric carboxylic acid capable of forming a dye at the places of the silver image upon being contacted with a color forming developer, said highly polymeric carboxylic acid derivative consisting of a chain-molecule wherein the color forming group recurs periodically linked to recurring carboxylic acid groups.

3. A photographic'silver halide gelatin emulsion containing a dyestufi component fast to diffusion with respect to the gelatin; said. dyestuff component being an amide of a color former with a highly polymeric carboxylic acid capable of forming a dye at theplaces of the silver image upon being contacted with a color forming developer, said dyestufi component being an acid amide from meta-aminophenylmethylpyrazolone and an interpolymer from vinyl chloride and maleic acid anhydride.

4. A photographic silver halide gelatin emulsion containing a dyestufl component fast to diffusion with respect to the gelatin said dyestuff component being an amide of a color former with a highly polymeric carboxylic acid capable of forming a dye at the places of the silver image upon being contacted with acolor forming dc vloper, said dyestufi component an acid amide from 1.5-aminonaphthol and an inter-- polymer from vinyl chloride and maleic acid anhydride 5. A photographic silver halide gelatin emulsion containing a dyestuflc component fast to difiusion with. respect to the gelatin, said dyestufl component being an amide of a color former with a highly polymeric carboxylic acid capable of forming a dye in situ with the reduced silver image.

6. A photographic silver halide gelatin emulsion containing a dycstufi component fast to diffusion with respect to the gelatin, said dyestufi component being an amide of a color former with a highly polymeric carboxylic acid in which the color former group recurs periodically, and being capable of forming a dye at the places of the silver image upon being contacted with a color forming developer.

'7. A photographic silver halide gelatin emulsion containing a dyestuif component fast to dii fusion with respect to the gelatin, said dyestuff component being an amide of a color former with a highly polymeric carboxylic acid, said highly polymeric. carboxylic acid derivative consisting of a carbon chain molecule wherein the color forming group recurs periodically in pairs, each group of a pair beingpnnited by an acid amide linkage to adjacent carbon atoms of said chain.

WILHELh I SEER. MAX mama-Donn. 

